CN115260454B - 一种聚芴型共轭聚电解质及其制备方法和应用 - Google Patents
一种聚芴型共轭聚电解质及其制备方法和应用 Download PDFInfo
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- 229920000867 polyelectrolyte Polymers 0.000 title claims abstract description 54
- 229920002098 polyfluorene Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- 230000001699 photocatalysis Effects 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 239000013535 sea water Substances 0.000 claims abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- RJIWYGUYDXBQCJ-UHFFFAOYSA-N 3-[2,7-dibromo-9-[3-(dimethylamino)propyl]fluoren-9-yl]-n,n-dimethylpropan-1-amine Chemical compound C1=C(Br)C=C2C(CCCN(C)C)(CCCN(C)C)C3=CC(Br)=CC=C3C2=C1 RJIWYGUYDXBQCJ-UHFFFAOYSA-N 0.000 claims 1
- 238000004062 sedimentation Methods 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 5
- 239000003426 co-catalyst Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
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- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 7
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- -1 Fluorene-9, 9-diyl Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- 238000005286 illumination Methods 0.000 description 5
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
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- 230000009467 reduction Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
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- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 239000012044 organic layer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- FCMCDVRJVMDKAQ-UHFFFAOYSA-N 1-chloro-n,n-dimethylpropan-1-amine;hydrochloride Chemical compound Cl.CCC(Cl)N(C)C FCMCDVRJVMDKAQ-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AVXFJPFSWLMKSG-UHFFFAOYSA-N 2,7-dibromo-9h-fluorene Chemical compound BrC1=CC=C2C3=CC=C(Br)C=C3CC2=C1 AVXFJPFSWLMKSG-UHFFFAOYSA-N 0.000 description 1
- RXACYPFGPNTUNV-UHFFFAOYSA-N 9,9-dioctylfluorene Chemical compound C1=CC=C2C(CCCCCCCC)(CCCCCCCC)C3=CC=CC=C3C2=C1 RXACYPFGPNTUNV-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 238000012856 packing Methods 0.000 description 1
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- 235000011056 potassium acetate Nutrition 0.000 description 1
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Abstract
本发明公开了一种聚芴型共轭聚电解质及其制备方法和应用。该聚芴型共轭聚电解质具有式(I)所示结构。本发明提出的聚芴型共轭聚电解质表现出明显增强的光生电荷传输及更低的荧光发射强度,在不添加任何共催化剂的情况下,制氢速率达到了1806μmol h‑1 g‑1,在光催化天然海水分解产氢领域具有良好的开发价值。
Description
技术领域
本发明属于天然海水光催化制氢领域,具体涉及一种聚芴型共轭聚电解质及其制备方法和应用。
背景技术
太阳光驱动下水分解产生氢气是获取清洁能源的有效途径,具有技术简单、环保的优点,引发了人们极大的研究兴趣。在过去的几十年中,成百上千种光催化材料被开发用于水分解产氢研究,其中绝大部分光催化体系所使用的水为纯水,而天然海水在地球中储量极为丰富,占水资源总量的97%。因此,发展直接利用来源广泛的天然海水分解产氢对于规模化工业应用无疑更具发展前景。但由于天然海水中存在复杂的离子和各种各样的杂质,使得发展高效稳定的光催化剂目前仍面临极大的挑战。
到目前为止,直接利用天然海水分解制氢的光催化剂报道还很少,且大多为杂化材料。聚合物光催化材料具有优异的光电性质,并且能够通过分子结构修饰进行灵活调控,近年来在光催化水分解领域引起了研究人员的广泛关注。相比传统无机半导体光催化材料,有机共轭聚合物由轻质元素组成,并且能够在温和的条件下合成得到。但是,有机聚合物在天然海水产氢领域却鲜有报道。最近,Sukumaran Santhosh Babu课题组报道了一系列金属卟啉基二维聚合物,用于太阳能海水分解研究。他们发现,以三乙醇胺为牺牲剂,含钴和镍的聚合物在不添加Pt共催化剂的情况下平均产氢速率为65 µmolh-1g-1。显然,目前所报道的聚合物海水产氢速率还很低,限制了其进一步实际应用,因此迫切需要开发新一代高效的聚合物用于光催化海水分解产氢。
发明内容
为了解决上述问题,本发明首次报导了一种聚芴型共轭聚电解质,其表现出明显增强的光生电荷传输及更低的荧光发射强度,在不添加任何共催化剂的情况下,制氢速率能够达到1806 µmolh-1g-1,在光催化天然海水分解产氢领域具有良好的开发价值。具体方案如下:
一种聚芴型共轭聚电解质,其结构如式(I)所示:
式(I);
其中R为H。根据本领域常识可知n为聚合度,无需限定具体数值。
本发明还提供了上述聚芴型共轭聚电解质的制备方法,包括以下步骤:
(1)将单体M1、单体M3和Pd(PPh3)4溶于溶剂中,在氩气保护下于100 ℃搅拌反应48h,冷却至室温后,有机层进行水洗,然后旋除大部分甲苯,所得残余物缓慢滴入甲醇中沉降,纯化后干燥,得到高分子P2;
单体M1为3,3'-(2,7-二溴-9H-芴-9,9-二基)双(N,N-二甲基丙烷-1-胺);单体M3为2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-9,9-二氢芴;溶剂为甲苯和2 M的碳酸钾水溶液的混合液;
(2)将高分子P2溶于THF中,然后加入溴乙烷和DMSO,在50 ℃的条件下搅拌反应5天,随后去除THF和溴乙烷,于乙酸乙酯中沉淀并过滤,得到粗品,将粗品通过氯仿和THF洗涤,干燥后得到所述聚芴型共轭聚电解质。
作为优选地,步骤(1)中,单体M1:单体M3:Pd(PPh3)4:甲苯:碳酸钾水溶液:甲醇=1.0 mmol:1.0 mmol:1.0 mmol:20 mL:5 mL:50 mL。
作为优选地,步骤(1)中,用丙酮洗涤三次进行纯化。
作为优选地,步骤(2)中,高分子P2:THF:溴乙烷:DMSO=100 mg:30 mL:1.5 mL:10mL。
作为优选地,干燥均为真空干燥。
本发明的有益效果为:本发明首次报导了一种聚芴型共轭聚电解质,其表现出明显增强的光生电荷传输及更低的荧光发射强度,在不添加任何共催化剂的情况下,制氢速率达到了1806 µmolh-1g-1,在光催化天然海水分解产氢领域具有良好的开发价值。
附图说明
图1所示为聚芴型共轭聚电解质分子结构;
图2所示为单体和共轭聚电解质合成路线;
图3所示为聚电解质在甲醇溶液和薄膜态下紫外吸收图和聚电解质甲醇溶液荧光发射图;
图4所示为聚电解质的XRD图;
图5所示为聚电解质循环伏安曲线、HOMO/LUO 能级及水分子氧化还原电势、在0.5M硫酸钠水溶液中的光电响应及电化学阻抗谱;
图6所示为PFNH-Br、PFN-Br和PFPABr在CH3OH/Et3N/seawater (1/1/1,v/v)混合液中照片;
图7所示为聚电解质在模拟太阳光下光催化产氢速率、光催化产氢循环测试、不同牺牲剂下光催化产氢性能图和不同波长单色光下的AQY及其紫外吸收光谱图;
图8所示为循环测试后PFNH-Br在DMSO中的1H NMR;
图9所示为P2的1H NMR;
图10所示为PFNH-Br的1H NMR;
图11所示为PFN-Br的1H NMR;
图12所示为PFPABr的1H NMR。
具体实施方式
以下将结合实施例和附图对本发明的构思及产生的技术效果进行清楚、完整的描述,以充分地理解本发明的目的、方案和效果。所有溶剂和试剂均从试剂公司购得,如无特别说明,纯度均为分析纯级。天然海水来自中国深圳南海,使用前经过简单过滤以去除泥沙和沉淀物。
实施例1:
PFNH-Br、PFN-Br和PFPABr(结构如图1所示)的制备:
相关合成步骤如图2所示。单体M1(3,3'-(2,7-二溴-9H-芴-9,9-二基)双(N,N-二甲基丙烷-1-胺)) 通过2,7-二溴-9H-芴和N,N-二甲氨基氯丙烷盐酸盐之间的烷基化反应合成得到,反应时需要加入浓NaOH水溶液。单体M2(3,3'-(2,7-双(4,4,5,5-四甲基-二氧硼戊环-2-基)-9H-芴-9,9-二基)双(N,N-二甲基丙烷-1-胺))合成时首先在-78℃下拔除芴单元9号位上的溴原子形成锂盐,随后加入过量的2-异丙氧基-4,4,5,5-四甲基-1,3,2-二氧硼烷得到目标单体。单体M3(2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-9,9-二氢芴)和M4(2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-9,9-二辛基芴)是通过相应的溴代物与联硼酸频哪醇酯在醋酸钾存在下90℃反应12 h得到。为了取得高反应产率,必须保证无水条件并且联硼酸频哪醇酯相对溴代物的用量是过量的。单体M1和M2通过Suzuki聚合反应生成中性前体高分子P1(聚({9,9-双[3’-(N,N-二甲基氨基)丙基]-2,7-芴}))。高分子P2(聚[(9,9-双(3’-(N,N-二甲基氨基)丙基)-2,7-芴)-alt-2,7-(9,9-二氢芴)])和P3(聚[(9,9-双(3’-(N,N-二甲基氨基)丙基)-2,7-芴)-alt-2,7-(9,9-二辛基芴)])由M1分别与M3和M4通过 Suzuki聚合反应得到。该反应以Pd(PPh3)4为催化剂,在甲苯与 K2CO3(2mol/L)水溶液中进行,反应液回流并保持充分搅拌。随后通过在氩气氛围下THF/DMSO混合溶剂中加入溴乙烷将中性高分子转化成离子型共轭聚电解质。
PFNH-Br的具体合成步骤为:
(1)将单体M1(1.0 mmol,494.3 mg)、单体M3 (1.0 mmol,418.1 mg)和Pd(PPh3)4(1.0% mmol,11.5 mg)溶于20 mL 除氧的甲苯和5 mL K2CO3水溶液(2 M)中,在氩气保护下于100 ℃搅拌反应48 h,冷却至室温后,有机层水洗三次,随后旋除大部分甲苯,所得残余物缓慢滴入50 mL甲醇中沉降出高分子粗品,随后用丙酮洗涤三次对高分子进行纯化真空干燥得445.6 mg淡黄色固体(高分子P2),产率89%;GPC结果:M w=22380,M n=14760, PDI=1.90.P2在氘代氯仿中的1H NMR如图9所示,具体为1H NMR (400 MHz, CDCl3):δ7.94-7.69(m, 9H),4.11-4.02 (m, 2H),2.25-2.04 (m, 33H), 1.31-1.25 (m, 10H), 0.99-0.84(m, 5H).
(2)将100 mg高分子P2溶于30 mL TMF中,然后加入1.5 mL溴乙烷和10 mL DMSO,在50 ℃的条件下搅拌反应5天,随后旋除TMF和过量的溴乙烷,然后于乙酸乙酯中沉淀并过滤,得到粗品,将粗品通过氯仿和TMF洗涤,真空干燥后得到48 mg黄色固体(PFNH-Br),产率43%。PFNH-Br在DMSO中的1H NMR如图10所示,具体为1H NMR (400 MHz, DMSO-d 6):δ8.12-7.61 (m, 9H),4.16 (s, 2H), 3.09 (s, 3H), 2.79 (s, 5H),1.23 (s,2H),1.02 (s,3H).
合成得到的PFNH-Br、PFN-Br和PFPABr通过1H NMR波谱进行结构表征,PFN-Br和PFPABr在DMSO中的1H NMR分别如图11和图12所示。三个聚电解质在化学位移7.58-8.24ppm有多重峰,归属于高分子芴单元的苯,另外,2.51-3.14 ppm和0.75-1.44 ppm处峰分别归属于-NCH2CH3中的亚甲基和甲基。PFNH-Br在化学位移4.16ppm处有一个单峰,归属于聚电解质主链上芴单元9位H原子。值得注意的,由于带电侧链的存在,所有聚电解质在醇等极性溶剂中具有优异的溶解性。
实施例2:
PFNH-Br、PFN-Br和PFPABr的光学性质:
(1)表征
PFNH-Br、PFN-Br和PFPABr在甲醇溶液和薄膜下的紫外吸收光谱如图3(a-c) 聚电解质在甲醇溶液和薄膜态下紫外吸收d) 聚电解质甲醇溶液荧光发射图,溶液浓度为50uM)和表1所示。三个聚电解质在甲醇溶液中紫外吸收相似,最大吸收峰位于385 nm左右。相比之下,薄膜态下PFNH-Br,PFN-Br和PFPABr的紫外吸收分别红移了5 nm,10 nm和4 nm,表明取代基团的类型对聚合物骨架的堆积具有一定的影响, 这也可以通过射线衍射图(XRD)进行佐证。如图4所示,PFNH-Br在2θ=~19°表现出一个相对窄的结晶峰,而PFN-Br和PFPABr衍射峰均较宽,可能是由于PFNH-Br在聚集态下共轭骨架具有更强的堆积。
聚电解质的光学带隙(Eopt,g)通过紫外吸收光谱的吸收边界进行估算,PFNH-Br,PFN-Br和PFPABr的光学带隙依次为2.86 eV,2.88 eV和2.84 eV。聚芴型共轭聚电解质主链取代基类型对其荧光发射性质也能产生影响。相比烷基取代的PFN-Br,主链含离子化侧链的PFPABr荧光较弱,而主链上H取代的PFNH-Br 表现出最弱的荧光。PFNH-Br更大的荧光淬灭表明其光生载流子复合受到抑制,有利于其产生更高的光催化活性。
(2)电化学测试
三个聚电解质的HOMO-LUMO能级通过循环伏安法进行测定,聚电解质的电化学测试在室温下无水乙腈溶液中进行,0.1 mol/L 四丁基六氟磷酸胺(Bu4NPF6)作为支持电解质,采用氮气鼓泡除氧,扫描速度为50 mV/s。聚电解质修饰的玻碳电极作为工作电极,铂电极作为对电极,Ag/Ag+电极(0.01 M AgNO3和Bu4NBF4乙腈溶液)为参比电极。加入Fc/Fc+对聚电解质电势进行校正。使用公式ENHE=EFc/Fc++0.63 V将Fc/Fc+氧化还原电势转化为标准氢电极电势。
相关结果如表1和图5(a)聚电解质循环伏安曲线;b)聚电解质HOMO/LUMO 能级及水分子氧化还原电势(vs. NHE, pH=0);c)聚电解质在0.5 M硫酸钠水溶液中的光电响应;d)电化学阻抗谱)所示。PFNH-Br的还原电势为-1.0 V,PFN-Br和PFPABr的还原电势略低,分别为-1.03和-1.04 V(图5a)。因此,计算得到PFNH-Br的HOMO/LUMO能级为-0.34/2.52 eV(vs.NHE),PFN-Br为-0.4/2.48 eV (vs.NHE),PFPABr为-0.34/2.52 eV (vs.NHE)。图5b展示的是三个聚电解质HOMO/LUMO能级相对水分解的氧化还原电势。如图5所示,三个聚电解质的LUMO能级负于水分子还原的电势,表明三个聚电解质热力学上均能催化水分子还原产生氢气。
(3)光电化学测试
为了揭示聚电解质光催化动力学,在三电极体系中进行了光电化学测试。所用电化学工作站是上海晨华CHI 852C。首先将聚电解质溶液滴涂在FTO导电玻璃上,自然晾干成膜并以此为工作电极。饱和Ag/AgCl 电极和铂电极分别为参比电极和对电极,0.5 M Na2SO4水溶液为电解质溶液。线性扫描伏安曲线测试时扫速为10 mV s−1,扫描范围为-1.0 V to1.0 VvsAg/AgCl。电化学阻抗谱 (EIS) 测试时频率范围为100 mHz到100 kHz,偏压为+0.6V (vsAg/AgCl)。
如图5c所示,在可见光下,聚电解质光电极快速产生光电流并达到稳定值,当关闭光源之后,光电流迅速回落。相比PFN-Br和PFPABr,PFNH-Br表现出最高的光电流,表明其光生载流子传输效率最高,这个结论也可通过图3d的荧光发射行为得到佐证。聚电解质的光生载流子传输阻抗通过电化学阻抗谱(EIS)进行研究。如图5d所示,相比PFN-Br和PFPABr,PFNH-Br尼奎斯特曲线弧半径最小,表明其载流子传输阻抗更低,电子传输效率更高。这个趋势与光电流响应结果是一致的,因此PFNH-Br有望达到更高的光催化活性。
表1
Polyelectrolyte | λabs(nm)a) | λabs(nm)b) | λonset(nm)a) | λem(nm)a) | Opticalgap(eV)b) | Ered,onset(V)c) | LUMO/HOMO (V,vs NHE)d) | HER(µmol h-1 g-1)e) |
PFNH-Br | 382 | 386 | 433 | 424 | 2.86 | -1.0 | -0.34/2.52 | 1806 |
PFN-Br | 390 | 400 | 431 | 417 | 2.88 | -1.03 | -0.4/2.48 | 356 |
PFPABr | 387 | 391 | 436 | 416 | 2.84 | -1.04 | -0.41/2.43 | 225 |
其中,a)甲醇溶液;b)通过公式Eg=1240/λonset计算,λonset为吸收边界;c)在无水乙腈溶液中测试,相对Fc/Fc+,0.1 Mn-Bu4NPF6为支持电解质;c)Ered,onset通过公式ENHE=EFc/Fc++0.63 V计算;d)通过公式EHOMO=ELUMO−Eg,opt计算。
(4)光催化产氢测试
测试了三个聚电解质在模拟太阳光条件下分解天然海水产氢的性能,光源为300W氙灯。在反应液中加入甲醇以帮助聚电解质在天然海水中分散。Et3N用作牺牲剂消耗光催化过程中产生的空穴。具体为:10 mg共轭聚电解质在超声下分散在2 mL CH3OH和2 mL H2O混合液中。然后加入1 mL Et3N作为牺牲剂。搭配模拟太阳光滤光片的300 W氙灯为光源,光照强度调整为100 mW/cm2。光催化反应在20 mL密封玻璃管中进行,光照前通N2二十分钟以除去反应瓶中的空气。析出的氢气通过装配TCD检测器的气相色谱(磐诺A60,中国)进行定量分析。溶于反应液中的微量H2忽略不计。表观量子效率用以下公式进行计算:AQY(%)=Number of reacted electrons/Number of incident photons×100% = 2×N×NA×h×C/(S×E×t×λ)×100%,其中N是析出氢气的物质的量(mol);NA是阿伏伽德罗常数(6.023×1023mol-1);h普朗克常量(6.626×10-34J·s);C是光在真空中传播的速度(3×108ms-1);S是光照面积(3.14 cm2);E是入射单色光强度(W cm-2);t是光照时间(s);λ单色光波长(m)。入射光强度通过光功率计进行测定。
值得注意的是,加入Et3N后海水中的杂质易于析出并在反应液中形成很多絮状物(图6)。这与纯水体系中是不同的,纯水体系中聚电解质能够很好地分散在三乙胺、甲醇和水混合液中。不添加聚电解质催化剂时没有检测到氢气生成。加入聚电解质后,随着光照时间的延长,氢气产量稳步增加。PFNH-Br 表现出最高的光催化产氢速率,达到1806 µmolh- 1g-1,而PFN-Br和PFPABr 光催化产氢速率分别为356 and 225 µmolh-1g-1。PFNH-Br的光催化性能比目前报导的有机光催化剂在相似条件下高很多。这个结果表明聚芴型共轭聚电解质主链上H基取代有助于显著提高其光催化性能,原因可能在于其显著提高的光生载流子传输。如图7a所示,在添加聚电解质之后,氢气产量随着照射时间的增加线性增加。PFNH-Br产氢速率最高,可达1806 µmol h-1g-1,而PFN-Br和PFPABr产氢速率分别为356和225 µmolh-1g-1。结果表明,芴基聚电解质骨架中用H取代有助于其光催化活性的提升,这可能时由于其光生载流子传输效率得到显著改善。图7b展示的是PFNH-Br在五次循环中的产氢稳定性。如图所示,PFNH-Br 能够在三次循环中稳定产生氢气,样品保留3天后重新测试,其结果与之前的几乎一致。循环测试后回收PFNH-Br进行1H NMR测试发现其化学结构几乎未发生改变,表明其在光催化过程中良好的稳定性(图8)。随后研究了PFNH-Br在不同牺牲剂下的光催化产氢性能(图7c)。当牺牲剂为二乙胺或抗坏血酸时仅能检测到极少量氢气,而牺牲剂为TEOA和EDTA-2Na时,光催化产氢速率分别为587和396 µmolh-1g-1。为了证明PFNH-Br产生的氢气是吸收太阳光造成的,我们测试了不同波长单色光下的表观量子效率。如图7d所示,PFNH-Br在400 nm和450 nm 处的AQY分别是1.52%和0.15%。
以上所述,只是本发明的较佳实施例而已,本发明并不局限于上述实施方式,只要其以相同的手段达到本发明的技术效果,都应属于本发明的保护范围。在本发明的保护范围内其技术方案和/或实施方式可以有各种不同的修改和变化。
Claims (8)
1.一种聚芴型共轭聚电解质,其特征在于,其结构如式(I)所示:
其中R为H。
2.一种权利要求1所述的聚芴型共轭聚电解质的制备方法,其特征在于,包括以下步骤:
(1)将单体M1、单体M3和Pd(PPh3)4溶于溶剂中,在氩气保护下于100℃搅拌反应48h,冷却至室温后,有机层进行水洗,然后旋除大部分甲苯,所得残余物缓慢滴入甲醇中沉降,纯化后干燥,得到高分子P2;
单体M1为3,3'-(2,7-二溴-9H-芴-9,9-二基)双(N,N-二甲基丙烷-1-胺);单体M3为2,7-双(4,4,5,5-四甲基-1,3,2-二氧硼戊环-2-基)-9,9-二氢芴;溶剂为甲苯和2M的碳酸钾水溶液的混合液;
(2)将高分子P2溶于THF中,然后加入溴乙烷和DMSO,在50℃的条件下搅拌反应5天,随后去除THF和溴乙烷,于乙酸乙酯中沉淀并过滤,得到粗品,将粗品通过氯仿和TH F洗涤,干燥后得到所述聚芴型共轭聚电解质。
3.根据权利要求2所述的制备方法,其特征在于,步骤(1)中,单体M1:单体M3:Pd(PPh3)4:甲苯:碳酸钾水溶液:甲醇=1.0mmol:1.0mmol:1.0mmol:20mL:5mL:50mL。
4.根据权利要求2所述的制备方法,其特征在于,步骤(1)中,用丙酮洗涤三次进行纯化。
5.根据权利要求2所述的制备方法,其特征在于,步骤(2)中,高分子P2:THF:溴乙烷:DMSO=100mg:30mL:1.5mL:10mL。
6.根据权利要求2所述的制备方法,其特征在于,干燥均为真空干燥。
7.权利要求1所述的聚芴型共轭聚电解质在光催化海水制氢中的应用。
8.根据权利要求7所述的应用,其特征在于,制氢速率为1806μmol h-1g-1。
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